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Selected inventionsA method of drilling mud treatment.USSR Author’s Certificate # 929682, 1974 Mamadzhanov U.D., Bakhir V.M., Shamsutdinova V.N., Bakhir T.M. The priority of this invention in accordance with Application # 2018444 was established on April 22, 1974. By that time, a two-year period of investigations and industrial tests of electrochemical methods of and devices for drilling mud treatment, which became the basis for electrochemical activation technology, had been over. The above investigations had been performed from 1972 in the Central Asian Research Institute of Natural Gas (SredAzNIIGaz). Drilling mud is a complex poly-disperse system containing clayey mineral particles in water with added organic substances - stabilizers, structure forming agents, thinners and fluid loss additives. The main technological function of drilling mud is bringing drill cuttings from the well bottom to the surface. Clayey particles in drilling mud are normally negatively charged, the charge density depending on surface configuration and chemical composition of clayey particle crystal lattice, as well as on chemical composition and electrolyte content of the liquid phase of drilling mud. Passing current through drilling mud commonly results in deposition on the anode of firm clayey crust made up of the most fine-disperse and highly-charged clayey particles. This crust prevents products of anode electrochemical reactions from entering the drilling mud, therefore the solution’s ðÍ value increases due to cathode, actually unipolar, electrochemical treatment. It was found that in conditions of the same consumed quantity of specific power, the smaller the cathode area as compared to the anode one, the stronger thixotropic properties of drilling mud (structural-mechanic strength) with simultaneously lower dynamic viscosity (paradox). The paradox can be explained in the following way: electric charges accumulated on the edges and pointed parts of tiny scales or needle-like particles of argillaceous minerals are several times stronger than the charges on their flat facets. Under the influence of electrochemical treatment, in a high voltage electric field close to the cathode surface (in the area of spatial charge), there increased absolute value of particles’ negative charge, thus enhancing their repulsion forces and therefore lowering viscosity. At the same time, however, difference of potentials between the edges and facets of argillaceous particles also increased, causing growth of forces putting in good order structural arrangement of interacting clayey particles. So, drilling mud’s structural and mechanical properties improved due not to mechanical, but to electrostatic adhesion of clayey particles. Investigation of the phenomenon in question both in laboratory and in conditions of real life drilling made it possible to understand specific nature of the processes observed, that is, nonequivalence of electrochemical and chemical regulation methods, and attempt practical application of the discovered effect in the process of oil and gas well drilling. The reported effect had not been known before, therefore the process of unipolar cathode electrochemical treatment of drilling mud was first called by V.M. Bakhir low-voltage polarization, and three years later –electrochemical activation. The above-indicated first invention established a non-chemical method to improve drilling mud parameters by treatment in an engineering electrochemical system consisting of a current power supply and two electrodes, the cathode surface area being smaller than the anode one. In this electrochemical system, the surfaces of drilling rig circulation system coming into contact with drilling mud actually performed the function of anode. Practical trials proved the method’s high efficiency, which allowed saving up to 30 % of chemical reagents commonly used for a well drilling. However, the method had a significant disadvantage, that is, the necessity to periodically remove clayey crust from anode surface and laboriousness of this procedure. Many other inventions of 1974-1976 not included in the given short list were aimed at further improvement of the discovered method of drilling mud parameters’ control, and technical systems for its implementation. Devices developed at that period were fitted with electrochemical reactors having flat electrodes (steel cathodes, magnetite or graphite anodes) with considerable surface area of a single electrode (from 0.2 to 0.7 m2) intended for high-ampere currents (600-1500 À) to treat large volumes of drilling mud (20-90 liters per second). Monitoring the operation of pilot devices in conditions of drilling deep oil and gas wells revealed that the larger mud volume coming directly into contact with the surface of working (negative) electrode, the higher the degree of drilling mud alterations observed after electrochemical treatment. Interelectrode space of the devices for unipolar (cathodic) electrochemical treatment was not partitioned by a diaphragm. In all modifications of devices developed to implement the effect of unipolar electrochemical exposure, positive electrode with dense clayey crust deposited on it was safely protected by the latter from direct contact with the main bulk of drilling mud. The products of anode electrochemical reactions did not enter the drilling mud as they accumulated in argillaceous solution crust whose thickness generally ranged between 2 and 3 cm. A method to control physical and chemical properties of drilling mudUSSR Author’s Certificate # 1035047, 1979. Bakhir V.M. The given invention whose priority was registered on March 26, 1979, actually contains the first published reference to anomalous change of the oxidation-reduction potential value of electrolyte aqueous solution after unipolar electrochemical exposure. The effect of anomalous change of water and drilling mud redox potential value due to such exposure was discovered by the invention’s author in 1975, however, it took quite a time to thoroughly investigate and substantiate the significance of measuring the above-mentioned parameter as indicator in the processes of liquid electrochemical activation. Under the classical approach, measuring the redox potential value of water or diluted aqueous solutions of several electrolytes is useless since it is impossible to distinguish a potential-defining reaction and to find a concrete chemical composition of redox couple. The given invention, contrary to the classical approach, for the first time indicates experimentally determined by the author variation range of electrolyte aqueous solution (drilling mud) redox potential due to unipolar (cathodic) electrochemical exposure: from + 100 ... + 200 mV to –800 ... –1000 mV (measured with the help of platinum electrode as compared to silver chloride reference electrode). From that time on, measuring redox potential value in water and diluted aqueous solutions of electrolytes subjected to unipolar electrochemical exposure has become a routine procedure performed by practically all researchers. A method of producing liquid possessing biologically active properties.USSR Author’s Certificate # 1121905, 1121906, 1121907, 1981. Vakhidov V.V., Mamadzhanov U.D., Kasymov A.Kh., Bakhir V.M., Alyokhin S.A., Iskhakova Kh.I., Baibekov I.Ì., Ovchinnikov I.V., Mariampolsky N.À., Goncharov P.V. The three above indicated inventions were the first published data sources on medical application of electrochemically activated water and solutions, which defined the role of electrochemically activated water and solutions as regulators of metabolic processes in the body of man and animals (# 1121906), as a factor stimulating the processes of reparatory and physiological regeneration (# 1121905), and as an antimicrobial, universal in its scope of action and non-toxic agent (# 1121907). A method of producing unsaturated hydrocarbons and benzene.USSR Author’s Certificate # 1154930, 1982. Liakumovich À.G., Bakhir V.M., Lemaev N.V., Alyokhin S.À., Sakhapov G.Z., Kirpichnikov P.À., Grigorovich B.À. Implementation of the given technological process in industrial conditions does not require costly special adjustments in design and operational technology of commercial pyrolysis furnaces, or unipolar electrochemical treatment of hydrocarbon raw material before its being fed into a pyrolysis furnace in a special industrial high-voltage electrochemical reactor, developing of which is a complicated problem still not solved. The gist of the offered technology is cathodic electrochemical treatment of evaporative liquid, that is, water of mineralization not exceeding 5-7 mg/l at 15-17 kgf/cm2 pressure and temperature over 100 °Ñ, as a result of which its redox potential value is to become at least –600 ... –700 mV. Then water with high negative redox potential value is evaporated and the vapor is fed into pyrolysis furnace in full accordance with routinely used technological process. The result is a considerable increase in the output of ethylene, propylene, bivinyl, and benzene – by 20; 25; 65 and 82 per cent respectively. The given method was tested in practice in pyrolysis furnace at the “Ethylene” plant of the Production Association “Nizhnekamskneftekhim” in 1983. The industrial test results completely confirmed the results earlier obtained in laboratory conditions in experimental pyrolysis plant at the central research laboratory of the Production Association “Nizhnekamskneftekhim”. For industrial tests of the technology, two flow-through electrochemical reactors with concentrically mounted electrodes and a diaphragm were specially built, whose output was 5 tons of cathodically treated water per hour. The reactors’ anodes were rods of dense MPG-6 graphite, 1000 mm long and with 100-mm diameter. The diaphragm made of cement- asbestos pipe with 4-mm thick walls was positioned between the outer electrode – cathode, made of 12Õ18Í9Ò steel, and anode with 5-mm clearances on both sides of the diaphragm. Voltage fed to the reactor ranged between 600 and 750 V, at current varying from 50 to 80 A, water mineralization being 6 mg/l, temperature – 110-112 °Ñ, and pressure at the electrode chambers of the reactor – 15-16 kgf/cm2 at 0.3 kgf/cm2 pressure differential on the diaphragm. A method of preparing electrolyte for lead accumulator.USSR Author’s Certificate # 1213923, 1983. Kirpichnikov P.À., Liakumovich À.G., Fridman B.S., Gamer P.U., Zaitsev Yu.I., Knyazev A.F., Kuleshov N.P., Bakhir V.M., Spektor L.Ye., Atadzhanov A.R. Cathodically activated 0.01% sulfuric acid solution is poured into accumulator, after which it is brought to the desired density by adding concentrated sulfuric acid. Service life of new and spent accumulators increases by 15-45%, “charge – discharge” capacity by 20-30%. The method was experimentally tested in NPO QUANT (Moscow) in 1984. A device for electrochemical treatment of liquids.USSR Author’s Certificate # 1719316, 17.10.1986. Bakhir V.M., Spektor L.Ye., Zadorozhny Yu.G., Lysenko N.M., Rudinsky Ya.A. Experiments show that in the process of electrochemical transformation of diluted solutions in flow-through electrochemical reactors, there occurs significant differential pressure on the diaphragm, and if the diaphragm is made of materials such as belting, tarpaulin, chlorine, open-porous polyethylene, mipor, miplast, naphyon and other polymer materials, its deformation results in changes of electrode chamber configuration, which has a distinctly negative effect on the parameters of electrochemical exposure. It was decided to improve flow-through diaphragm-type electrochemical reactors by designing rigid structures with ceramic diaphragms. Electrochemical reactors with diaphragms made of various ceramic materials whose inner diameter ranged between 20 and 150 mm, wall thickness from 2.5 to 6.0 mm, and length between 200 and 450 mm, were tested. Experiments established the optimal ratio of anode and cathode diameters, the width of electrode chambers (the distance between electrode surface and diaphragm) and their length in the above indicated range of sizes, the material of electrode and diaphragm being the same as in the experiment. The given experiment is crucial, because it outlined the main direction of developing the design of flow-through diaphragm-type electrochemical reactors for unipolar treatment of water and diluted aqueous electrolyte solutions in the period between 1985 and 1989. The subject of the invention is a diaphragm-type flow-through reactor in the form of an electrode - monoblock, with in-built co-axially mounted counter electrodes and ceramic diaphragms. Anodes in these reactors were made of carbon coated by manganese dioxide or titanium coated by ruthenium oxide; cathodes – from carbon (solid graphite), diaphragms – from ceramics based on aluminum oxides, later – from zirconium oxide ceramics. The area of a single anode was 25-40% smaller than that of cathode and was 0.01-0.02 m2. Total electrode surface in an individual reactor achieved 1.0 m2. The said reactors, unlike those developed earlier, were capable of working in conditions of considerable differential pressure on the diaphragm. Systems designed at that time featured greatly improved specific performance characteristics of electrochemical reactors with considerable reduction of their weight and dimensions. Full-scale production of such systems revealed their high efficiency and further widened the scope of electrochemical activation technologies’ application extending to such spheres as, for instance, electronic industry, where technological processes require de-ionized (distilled) water. This type of electrochemical reactor had no analogues, and represented the third generation of flow-through diaphragm-type reactors with co-axially installed electrodes and diaphragms. It was used in many devices manufactured on a large scale: Use of ceramic diaphragms solved many difficult problems, but it gave rise to electro-osmosis problem, that is, electro-osmotic transfer of liquids through a porous hydrophilic diaphragm. Electro-osmotic transfers significantly complicated development of electrochemical systems with a closed volume of slowly replenished auxiliary electrolyte. A method of producing nitrogen fertilizers.USSR Author’s Certificate # 1594917, 1987. Bakhir V.M., Spektor L.Ye., Shtern K.L., Zadorozhny Yu.G., Gusakov N.I., Kiporenko A.G. The invention can be used for non-chemical and non-waste production of nitrates of alkaline and alkaline-earth metals from salts dissolved in water meant for irrigating crops. The substance of the invention is that irrigation water is subjected to cathodic treatment in electrochemical reactor, which results in its being enriched with sodium, potassium, calcium, magnesium, iron and other metal hydroxides generated from salts present in naturally mineralized water. The resulting irrigation water catholyte, before being fed for watering, is mixed with air, which passed through arc or powerful spark electric discharge. In the electric discharge in the air nitrogen oxides are formed, and being dissolved in water they generate nitric acid. Further development of a chain of chemical reactions takes place along the way of nitric acid interaction with metal hydroxides dissolved in water resulting in formation of a mixture of potassium, sodium, calcium, magnesium, iron and other metal nitrates in water. In spite of negligible concentration, nitrates synthesized in water in this manner are much more efficient due to synergic effect (mixed nitrates are more efficient than mono-substance). The invention was tested in the hothouses of Tashoblagroprom in 1987. Watering plants with water containing nitrogenous fertilizers freshly prepared in it was shown to reduce soil salinity, increase crop yield and lower the content of nitrates in fruits. In spite of complete exclusion of routinely used nitrogen fertilizers, the yield of ÒSKhÀ-211 cucumbers increased by 20%, the nitrate concentration in the cucumbers being twice as low as that in cucumbers grown according to commonly used technology. Electrochemical treatment of water and device for electrochemically treating water.British patent GB 2 253 860. Filed 12.03.91, published 23.09.1992. The patent’s authors are indicated in conformity with the Decision of the British Patent Bureau of January 13, 2000. V.M. Bakhir, Y.G. Zadorozhny. A flow-through electrochemical modular cell – FEM-1. FEM – 1 module was developed by V.M. Bakhir and Yu.G. Zadorozhny in 1989, and first prototypes were made and tested in the same year. FEM-1 module played an important role in development of a new approach to engineering and technology of producing electrochemically activated water and solutions. It was not used on a large scale in industry due to complexity of manufacturing collector heads and a number of problems associated with formation of bi-polar areas of cathode electrode surface, however, it indicated an optimal principal way of designing commercial electrochemical systems. Combined with auxiliary electrolyte capacity operated under elevated pressure, FEM-1 module was used in the first modification of STEL-ÌÒ-1 device meant for producing washing, disinfectant and sterilizing solution – anolyte with neutral ðÍ value. The device was developed in conformity with the Russian Ministry of Health assignment. It began in VNIIIMT MZ RF in October 1990 and finished in June 1992. The flow sheet was later described in the British Patent GB 2 253 860. Preparatory work for development of STEL-ÌÒ-1 device, that is, working out and putting into full-scale production FEM -1 module, had been carried out in VNIIIMT MZ RF by V.M. Bakhir and Yu.G. Zadorozhny from 1989. Based on the analysis of the documents confirming the above facts, in January 2000 the British Patent Bureau issued a decision to change the list of authors and to indicate only true authors (V.M. Bakhir and Yu.G. Zadorozhny) in the patent GB 2 253 860. An electrolytic method of drinking-water purification.British patent GB 2 257 982. Filed 24.07.1991, published 27.01.1993. The patent’s authors are indicated in conformity with the Decision of the British Patent Bureau of January 13, 2000. V.M. Bakhir, Y.G. Zadorozhny. The given invention is the first version of the technological water purification process in EMERALD device. The process of purification included consecutive stages of treating water flow in a system composed of one electrochemical module – FEM-1, or a unit made up of such modules – RPE reactor, with the purpose of its final purification. Source water was supplied to the anodic chamber of the reactor, and flowing through it became more acid and saturated with oxidants – products of water anodic decomposition, the main active substances of which are ozone, hydroperoxide and peroxide compounds, hypochlorous acid and other meta-stable chlorine-oxygen compounds. Time of water presence in the anodic chambers of EMERALD devices does not exceed one – two seconds, however, at 0.5-1.0 A current, this is sufficient for destruction of practically all microorganisms (including spores), harmful organic compounds and microbial toxins. Then water entered catalytic reactor filled with dense granules of carbon (graphite). Here occurred catalytic destruction of chlorine-oxygen compounds synthesized in water in the anodic chamber with generation of active oxygen forms. The conclusive stage of EMERALD technological process was electrochemical cathode treatment in reactor to bring water ðÍ value back to neutral and convert heavy metal ions into insoluble hydroxides with the purpose of their subsequent removal through filtering or precipitation. Regarding this patent, as was the case with the above-indicated British Patent GB 2 253 860À, in January 2000 the British Patent Bureau issued a decision to change the list of authors and to indicate only the true authors of the invention – V.M. Bakhir and Yu.G. Zadorozhny. After other technological processes of water purification had been developed, the authors decided to give the common name of EMERALD to all water purification devices supplied with electrochemical reactors made up of FEM modules, and distinguish them by the names of the corresponding technological water purification processes: EMERALD, SAPPHIRE, CRYSTAL, RUBY, AQUAMARINE, AMBER, QUARTZ, BERYL, TOPAZ and others. A device for electrochemical treatment of water.RF Patent # 2042639. Filed 03.04.1992, published 27.07.1995. Bakhir V.M., Zadorozhny Yu.G. A flow-through electrochemical modular cell of FEM-2 type, a flow-through electrochemical linear reactor of RPE-L type. Ideologically, FEM-2 module is evolution of FEM-1 module, however, technically it is an absolutely new device that essentially differs from its prototype – FEM-1 module. FEM-2 module is the first device with precisely indicated absolute and relative dimensions of electrode chambers, which is crucial for electrochemical treatment of low-mineralized electrolyte aqueous solutions and fresh water. It also considerably decreases risk of bi-polar areas’ emergence on electrode surfaces. The device can be commercially manufactured using plastic collectors made not by lathing as in case of FEM-1 module, but by casting plastic parts in press-molds. This was achieved thanks to a different structure of collector head end-points and, correspondingly, collector heads themselves. In the period of legal, that is, in conformity with license agreements and under the authors’ control, manufacture of FEM-2 modules (1992-1995), the joint Soviet-British venture EMERALD produced over 100,000 FEM-2 modules, which were used in STEL, EMERALD and other electrochemical systems. From 1995, FEM-2 module production, which had been under constant scientific and engineering control of the authors up to that time, along with the production of all electrochemical systems fitted with it, was stopped by the authors due to the development of the third generation of compact-size electrochemical diaphragm-type reactors - FEM-3 modules. A device for electrochemical treatment of water.RF Patent # 2038322. Filed 03.04.1992, published 27.06.1995. Bakhir V.M., Zadorozhny Yu.G., Leonov B.I., Vedenkov V.G. STEL device for producing electrochemically activated sterilizing, disinfectant and washing solutions - À, ÀN anolytes, Ê catholyte. The given engineering design was implemented in the second modification of STEL device – STEL-ÌÒ-1Ì. A distinctive feature of the electrochemical system was the presence of hydraulic resistances at the inlets of initial diluted table salt aqueous solution to the anodic and cathodic chambers of the reactor, and one hydraulic resistance at the outlet from the anodic chamber of electrochemical reactor. Adjusting the flow rate and electrode chamber pressure allows to produce acid anolyte with ðÍ below 5 (À anolyte), neutral anolyte with ðÍ from 6.0 to 7.5 (ÀN anolyte) and alkaline catholyte with ðÍ above (Ê catholyte). A drawback of the flow chart is the need to adjust the system upon each startup, or when changing operation regime, because of the necessity to control the end solutions’ parameters. The given device was manufactured by the Production-Engineering Complex “Medelektrokhimapparat” of NPO EKRAN on a large scale from 1992, and in two years (1992-1993) over 1,000 STEL-ÌÒ-1Ì devices were manufactured and delivered to consumers (Russian hospitals). A device for decontaminating and purifying water.RF Patent # 2040477. Filed 03.04.1992, published 27.07.1995. Bakhir V.M., Zadorozhny Yu.G., Rakhmanin Yu.À. EMERALD-S device for water purification, technological process of water purification including anodic treatment of water in a diaphragm-type electrochemical reactor with simultaneous removal of cations and subsequent dechlorination of water in a catalytic reactor. Through the cathodic chamber of reactor in EMERALD-S device there flows a modest initial water flow thanks to hydraulic resistance at its inlet. The pressure in the anodic chamber of the device is higher than that in the cathodic one by 0.3-0.4 kgf/cm2, which accelerates heavy metal ions’ removal from the flow of treated water due to their electromigrational transfer through the diaphragm, but does not prevent some amount of free hydroxyl groups from cathodic chamber from entering water flowing through the anodic chamber for its ðÍ value correction. A device for electrochemically treating water.International Application WO 93/20014. Filed 26.03.1993, published 14.10.1993, convention priority of 03.04.1992. Bakhir V.M., Zadorozhny Yu.G., Rakhmanin Yu.À., Naida I.N., Naida N.N., Dzheyranishvili N.V., Leonov B.I., Butin S.K. and Vedenkov V.G. The Application was made up by adding to the engineering solution described in RF patent # 2042639 (FEM-2 flow-through electrochemical modular cell, RPE-L flow-through electrochemical reactor), which is the main part of the invention, additional features from the engineering solutions of three RF patents (## 2038322, 2038323 and 2040477) – STEL-ÌÒ-1-, EMERALD –M-, EMERALD-S- type devices. For the four above-indicated inventions patented in Russia, exclusive license agreements were concluded in 1993 with the EMERALD company. In spite of the fact that the agreements did not envisage the inventions’ promotion to the market outside the Russian Federation without the patent-holders’ (V.M. Bakhir and Yu.G. Zadorozhny) approval, the Joint-Venture “Emerald” executives (Dzheyranishvili N.V.) without the patent-holders’ knowledge, via a number of dummy companies made an attempt to transfer the rights for using the said inventions to the British-American company, which, being very interested in V.M. Bakhir’s inventions, made an attempt to establish control over all V.M. Bakhir’s patents under the above-mentioned license agreements. Justice in the given case prevailed thanks to the decision of the Russian court, which terminated the license agreements with the “Emerald” company on 04.05.1995. A device for electrochemical treatment of water.RF Patent # 2078737. Filed 26.05.1994, published 10.05.97. Bakhir V.M. and Zadorozhny Yu.G. Flow-through electrochemical modular reactor – FEM-3 module. FEM-3 module, while very similar to FEM-2 module in the principle of its application in electrochemical systems, technically has an absolutely new design, and essentially differs from its prototype – FEM-2 module. Unlike FEM-2 and FEM-1 modules, FEM-3 module is devoid of problems arising in connection with the presence of bi-polar areas on the surface of external electrode, and it surpasses FEM-1 and FEM-2 modules in its mechanic, hydraulic and electrochemical reliability and durability. The Table below presents principal differences between FEM-1, FEM-2 and FEM-3 modules, which demonstrate advantages of FEM-3 module as a commercial standard all-purpose device for various types of electrochemical systems. FEM-3 module and RPE reactors made up of units of FEM-3 modules have the following typical feature. FEM-3 modules can be used to implement any technological processes developed for FEM-1 and FEM-2 modules. Simultaneously, performance characteristics of these processes become better. However, FEM-1 and FEM-2 modules cannot be used in process flow sheets developed for FEM-3 modules either due to reasons making such replacement technically and technologically impossible, or because performance characteristics of processes implemented with the help of FEM-1 or FEM-2 modules prove to be worse than when using FEM-3 modules. Principal technical and technological differences of FEM-1, FEM-2 and FEM-3 modules
In the process of further practical work with FEM-3 modules it was realized that the development of a reliable, all-purpose and easy-to-use electrochemical reactor marked the birth of the technology of electrochemical activation in particular, and the technology of “personal” applied electrochemistry in general. A device for producing washing and disinfectant solutions.RF Patent # 2088539. Filed 31.05.1995, published 27.08.1997 Bakhir V.M., Zadorozhny Yu.G., Barabash T.B. STEL device for production of electrochemically activated sterilizing, disinfectant and washing solution for the first time implements technological process of producing anolyte known as ANK. The first stage of the technological process of ANK production includes cathodic treatment of the whole bulk of initial sodium chloride solution, and after solution’s leaving the reactor’s cathodic chamber the second stage is carried out – separation of part of catholyte and hydrogen bubbles with adherent particles of heavy metal hydroxides, after which catholyte saturated with dissolved hydrogen and cleared from heavy metal ions undergoes subsequent treatment in the anode of the same electrochemical reactor. Technological process of ANK anolyte production realized in the given device is very simple and allows to produce efficient antimicrobial and washing solution in a flow-through diaphragm-type electrochemical reactor in the absence of differential pressure on diaphragm. According to a diaphragm classification well known in applied electrochemistry, diaphragm used in the process of ANK anolyte production is called submersible, that is, working in conditions of no differential pressure. On the contrary, electrochemical reactor diaphragm working under differential pressure is called filtration one. The seeming simplicity of the technological process is deceptive. For instance, in the course of ANK anolyte testing in the Research Institute of Disinfectology of the Ministry of Health of the Russian Federation (VNIID) and practical application of the first STEL devices in Russian medical facilities, experts in producing sodium hypochlorite in non-diaphragm electrolyzers had a lot of questions: “In the process of ANK anolyte production both cathodic and anodic treatment of initial salt solution take place, same as in non-diaphragm electrolyzers. What is the principal difference between the solutions obtained? Is ANK anolyte with ðÍ about 7 a hypochlorite solution? Can ANK anolyte be produced by adding a small amount of hydrochloric or some other acid to alkaline (with ðÍ above 8) sodium hypochlorite solution? Can ANK anolyte be produced by mixing anolyte with some catholyte? Why is ANK anolyte’s bactericidal ability 300 times higher than that of sodium hypochlorite solution, when oxidant (active chlorine) concentration is the same? Why does sodium hypochlorite solution have no sporicidal power at any concentrations, whereas ANK anolyte kills all existing spores and is sterilizing (i.å., eradicating all microorganism species and forms) at a concentration as low as 50 mg/l?” Answers to these questions are rather simple, but in the given paper they are only outlined and cannot be completely disclosed. The point is that in spite of subjecting initial solution to both cathodic and anodic treatment in the process of ANK anolyte production the principle of electrochemical exposure unipolarity is very strictly observed and realized by separating the processes of opposite-polar electrochemical treatment of the same portion of the solution in space and in time. When initial salt solution flows through the cathodic chamber of reactor, some part of chlorine ions is removed from it through the diaphragm due to electromigration. With oncoming movement through the diaphragm, sodium ions transport electric charge from solution flowing in the anodic chamber. Thus, under the action of electric current, during solutions’ flow through electrode chambers, there occurs fixation of increased (as compared to initial solution) sodium ion concentration in cathode chamber and increased (also in comparison to initial solution) chlorine ion concentration in anode chamber. After removing part of sodium ions along with a solution of mixed sodium, magnesium, calcium and iron hydroxides in a flotation reactor, solution containing sodium ions at a concentration lower than that of initial solution is fed into the reactor’s anodic chamber. The excess of chloride-ions in anodic chamber results in that they are the first to oxidize on the anode forming chlorine-oxygen compounds in ANK anolyte, and their concentration surpasses the concentration of salt formed in the equivalent quantity during chemical (or electrochemical – in non-diaphragm reactor) interaction of molecular chlorine with sodium hydroxide solution. This chemical instability of ANK anolyte is the most important factor of its biocidal activity. Achieving as high chemical instability of a solution as possible depends on many factors, in particular, on physical and chemical properties of electrochemical reactor diaphragm, its size, shape, ratio of dimensions of principal components of reactor’s electrode chambers, initial solution flow rate, salt content, current density and many other factors. At the present moment, over 30,000 STEL devices producing ANK anolyte operate in Russian medical facilities. However, many of these devices are imitations and cannot produce the kind of anolyte the authors meant. It happens because smart suppliers and manufacturers of fake STEL devices pay attention only to outward attributes of original technology and devices for its implementation, but provide their articles with official papers received after testing the original devices. It is extremely difficult to tell a fake device from a real one, especially for uninformed consumers. There are several companies having no legal rights to manufacture devices producing ANK anolyte, such as “Aquastel” company registered in Estonia and manufacturing “Aquastel” and “Eurostel” devices with reactors that do not violate the patent law, as they do not resemble FEM-1, FEM-2, and FEM-3 modules in their appearance, but cannot produce proper-quality ANK anolyte; “Perspektiva” company from Dubna, Moscow region, manufacturing fake FEM-3 modules, whose unsatisfactory work causes consumers’ complaints, as well as some other companies and individuals. A device for obtaining products of anodic oxidation of alkaline or alkaline-earth metal chloride solution.RF Patent # 2088693. Filed 9.02.1996, published 27.08.1997. Bakhir V.M. and Zadorozhny Yu.G. This invention protected by RF patent # 2088693 was the first publication in patent literature about a new technological process – ion-selective electrolysis with diaphragm and a device for implementation of the process. The essence of the process is electrochemical decomposition of a concentrated sodium chloride solution followed by generation of anodic oxidation products in the form of a gaseous mixture of oxidants – chlorine, chlorine dioxide and ozone, as well as products of cathodic reduction in the form of a concentrated (150-170 g/l) sodium hydroxide solution without preliminary conditioning of initial sodium chloride aqueous solution (only rough cleaning from hardness salts is needed) and intermediate (in the process of electrolysis) continuous conditioning of anolyte and catholyte in electrochemical reactor with ceramic inert microporous diaphragm. The technology of ion-selective electrolysis (ISED) was developed as an alternative to well-known technological processes of chlorine synthesis: electrolysis with a mercury cathode, electrolysis with diaphragm, and electrolysis with ion-selective membrane. The ISED technology was first realized in device called AQUACHLOR, and was meant for highly efficient and ecologically safe synthesis of a mixture of gaseous products – chlorine (95%), chlorine dioxide (3%), ozone (2%), as well as sodium hydroxide solution (150-170 g/l) from sodium chloride solution (200-250 g/l). The end products of AQUACHLOR devices are acid (with ðÍ 2.5-3.5) solution of above-mentioned oxidants in water with concentration from 0.5 to 2.0 g/l (an analogue of chlorine water generated in chlorinators at water treatment plants during gaseous chlorine introduction in water) and sodium hydroxide solution of 150-170-g/l concentration. AQUACHLOR device is supplied with electrochemical reactor of RPE type made as a combination of hydraulically connected in parallel FEM flow-through electrolytic modular cells, an appliance for feeding salt solution under pressure up to 2 kgf/cm2 into electrochemical reactor, and a current power supply. Anodic and cathodic electrode chambers of the reactor are hydraulically connected with anodic and cathodic circulation capacities. The anodic capacity of circulation circuit is fitted with upstream pressure controller. In the process of the device’s operation, a saturated sodium chloride solution under pressure is dosed into the anodic chamber of electrochemical reactor. This solution circulates throughout anodic chamber thanks to gas lift: gases liberated on anode – chlorine and chlorine dioxide – take liquid up with them, to a capacity where gas is separated from liquid. Gaseous mixture is removed from the upper part of the capacity, and the liquid returns to the inlet into anodic chamber. The pressure in the reactor’s anodic chamber is 0.5-1.0 kgf/cm2 higher than that in the cathodic one, preventing hydroxide ions from penetration from cathodic to anodic chamber and in this way increasing chlorine gas current output. Under the action of differential pressure and due to electro-diffusion transfer, sodium ions penetrate from anodic to cathodic chamber through diaphragm along with the solvent – water. Thus, in the cathodic chamber, concentrated alkaline solution is formed which circulates due to hydrogen gas lift. Excess of this solution is removed from the upper part of cathode circulation circuit capacity together with hydrogen. Consumption of salt present in the form of a saturated saline solution in the reactor is minimal – within the amount of solution filtered through the diaphragm into cathodic chamber. The degree of salt decomposition reaches 98 % since anodic process takes place in acid milieu under elevated pressure. Electrochemical reactor is supplied with voltage providing for flow of current through each FEM-3 module from 5 to 8 A (depending on the required output). Normally, each FEM-3 module of AQUACHLOR device reactor operates under 2.5-2.8 V pressure in the current strength range indicated above. Revolutionary importance of this invention inspired not only true enthusiasts but also persons skilled in stealing intellectual property. Thus, a certain Alexei Yuryevich Popov, who headed the firm “Tecton”, for some time was a partner of the LET (“Laboratory of Electrotechnology”, the founders – V. Bakhir and Yu. Zadorozhny). In co-authorship with his son, A.Yu. Popov filed an application for the same invention and, using loopholes in the Russian patent laws, received patent # 2110483, the rights to which he transferred to the anglo-american company at the stage of patent examination. Being an interested party the above company did not properly check the validity of the transferred rights, or, probably, did not consider necessary to do that, counting in advance that the risk of failure in the given situation is negligibly low taking into account the statistics of stolen Russian inventions. Patent holders for “AQUACHLOR” device did not initiate proceedings against A.Yu. Popov for intellectual property theft. Instead, they filed an objection against grant of Patent # 2110483. Rospatent’s Chamber of Appeal (now Patent Dispute Chamber) in its Decision of November 14, 2000, declared Patent # 2110483 of Popov invalid and annulled it completely. A method of indoor disinfection.RF Patent #2148414. Filed 29.10.1998, published 10.05.2000. Tsikoridze N.G., Bakhir V.M., Zadorozhny Yu.G., Yakovlev Yu.N., Maleev B.V., Panicheva S.A., Vtorenko V.I. The idea to apply electrochemically activated anolyte as a mist for indoor disinfection and disinfection of internal surfaces of large capacities was first suggested by Professor of the Georgian Institute of Subtropical Farming (GISF) Nodar Georgievich Tsikoridze in 1996. He initiated and headed research and development of the most efficient designs of dispersing systems securing preservation or even enhancement of anolyte aerosol biocidal action. Conducted research revealed that mixing anolyte with air in the process of its dispersion extremely negatively affected the aerosol’s anti-microbial activity. The results of testing various types of dispersers (liquid atomization by rapid air flow under vacuum and under pressure, liquid jet atomization under pressure on dispersant surfaces of differently shaped nozzles made of different materials, cavitation and ultra-sound dispersers) proved absolute superiority of spinning disk disperser in which a thin laminar layer of liquid (anolyte) was thrown from a peripheral edge of ceramic disk spinning at a high rate (up to 25,000 rpm) and was fractioned due to deceleration after collision with air. A method of non-chemical alteration of physical and chemical properties of water and/or water solutions.RF Patent # 2155717. Filed 28.01.2000, published 10.09.2000. Bakhir V.M. The given invention describes the principle and technology of non-contact electrochemical activation. Effect of non-contact action produced by electrochemically activated water and aqueous solutions on non-activated liquids was discovered by the author in 1987 and described in his monograph ”Electrochemical Activation” in 1992. The mechanism of this phenomenon is still unclear, however, under optimal combination of non-contact action conditions, several versions of which were found empirically, there is 100% recurrence of change of redox potential (to a higher degree) and electric conductivity (to a lesser degree) of water or aqueous solution of electrolytes, separated by impermeable thin dielectric partition from water or aqueous solution of electrolytes in a meta-stable (activated) state after unipolar (anodic or cathodic) electrochemical exposure. In the process of non-contact electrochemical activation, the ratio of volumes of activated and non-activated media separated by a dielectric partition, its material and thickness, area of interaction (area of dielectric partition) and contact duration are essential. The findings of experimental studies of non-contact electrochemical activation processes indicate that non-contact electrochemical exposure is a real possibility to purposefully regulate physical and chemical solution properties without altering their chemical composition. By controlling solutions’ redox potential it is possible to change their activity in oxidation-reduction reactions and in this way directly impact various technological processes. Besides, by purposefully regulating the redox potential of solutions entering the human body, for instance, beverages, solutions of medicinal agents or biological body fluids, we can enhance the positive effect on the organism of oxidation-reduction reactions occurring in the human body with participation of the above solutions and fluids. Electrochemical modular cell for treating aqueous solutions, device for obtaining products of anodic oxidation of alkaline or alkaline-earth metal chloride solution.RF Patent # 2176989. Filed 01.11.2000, published 20.12.2001. Bakhir V.M., Zadorozhny Yu.G., Leonov B.I., Panicheva S.A. The principal component of AQUACHLOR device meant for producing an oxidant mixture from sodium chloride solution is electrochemical reactor. The given patent for the first time in patent literature describes the reactor of AQUACHLOR device consisting of previously unknown FEM-7 flow-through electrochemical modular cells, each of which is a tiny diaphragm-type electrolyzer with co-axially mounted electrodes and a diaphragm. The outer electrode of FEM-7 module serves as cathode and is made of 35-cm-long titanium pipe 40 mm in diameter. The inner electrode (anode) is made of 29-cm-long titanium pipe 16 mm in diameter. The anode surface is coated with ruthenium and iridium oxides. As compared to routinely used ORTA electrodes, the anodic coating, all other working conditions being equal, has an 800-1500 times longer service life. The anodes in AQUACHLOR device reactor work under conditions very favorable for oxide coating: the ðÍ value of the medium in anodic chamber is always below 2.5. Experience of continuous five-year employment of anodes in AQUACHLOR device reactors demonstrated complete absence of coating wear signs. FEM-7 module’s ceramic diaphragm is made of mixed zirconium, aluminum and yttrium oxides, is exclusively resistant to the action of acids, alkali, oxidants and reductants; its tensile strength is up to 5 atmospheres and it has an unlimited service life. No diaphragm cleansing is required in the process of AQUACHLOR device operation, if softened saline solution is supplied to the devices. When used saline solution contains hardness salts, it is necessary to periodically clean the diaphragm with a 3% hydrochloric acid solution. The cleaning is performed by rinsing AQUACHLOR device reactor without its disassembly for 15 minutes. Unlike all other well-known processes of chlorine production from sodium chloride solution (diaphragm electrolysis, electrolysis with ion-exchange membrane, electrolysis with mercury cathode), in FEM-7 module of AQUACHLOR devices the process of sodium chloride decomposition into end products – a gaseous mixture of oxidants, sodium hydroxide solution of 150-170 g/l concentration (depending on initial saline solution concentration) and hydrogen – occurs during one cycle, i.å. without any return of anodic or cathodic products for repeated treatment into the reactor, and adding no water into the cathodic chamber. In other words, FEM-7 modules realize decomposition technology, the gist of which is that the entire volume of salt solution of 200-250 g/l concentration that enters the anodic chamber is completely (during one cycle) decomposed into humid gas (chlorine, chlorine dioxide, ozone), and in the cathodic chamber, with no extra water added, also during one cycle, sodium hydroxide solution with 150-170 g/l concentration (approximately, in the volume of incoming saline solution) and gaseous humid hydrogen are formed. The main technological characteristic of AQUACHLOR device is that synthesis of oxidants in the anodic chamber occurs under pressure considerably exceeding the pressure in the cathodic chamber (drop of about 1 kgf/cm2). Superposition and interaction of pressure gradients, electric field voltage, electrolyte concentration and density of current in porous space of relatively thick-walled ceramic diaphragm ensures removal of selective sodium ions together with excessive water from anodic chamber through the diaphragm into cathodic chamber; preservation of all chlorine ions in anodic chamber; and complete impossibility of hydroxyl anions penetrating from cathodic to anodic chamber. AQUACHLOR device can be easily adapted to a dc power supply of required wattage with practically any output current and voltage parameters, since the reactor’s design provides for a possibility of changing the electric circuit of FEM-7 connection. When FEM-7 modules are consecutively connected, the device’s reactor turns into a bipolar electrolyzer of original design, as electrochemical cells (FEM-7 modules) it consists of are spatially and galvanically separated from each other. When FEM-7 modules are connected in parallel, the reactor becomes a sort of monopolar electrolyzer. Mixed (consecutive-parallel) connection of FEM-7 modules in the reactor of AQUACHLOR device is also possible. The voltage on a single FEM-7 module in the process of work can be from 2.8 to 4.0 V, at current strength from 20 to 30 A, and initial saline solution mineralization varying from 200 to 250-300 g/l. The degree of salt decomposition is 99.3-99.8%. Therefore, actual specific consumption of salt for oxidant production in AQUACHLOR device is approximately 1.7 g per 1 g of oxidants. At current strength of 23-24 A, a FEM-7 module produces 30 g/h of oxidants (as molecular chlorine), voltage on it approaching 2.8-2.9 V, and specific energy consumption being about 2 kW per 1 kg of oxidants (chlorine). In this regime the share of molecular chlorine in liberated gas is 98 - 99%. To increase the share of chlorine dioxide and ozone in a mixture of synthesized oxidants to 3-7%, AQUACHLOR devices are used in more high-power conditions, that is, at current strength over 25 A on a single FEM-7 module, and voltage above 3 V. Specific energy consumption is, respectively, between 2.5 and 3.0, and can achieve 3.5 kW-h/kg in conditions of correspondingly increasing output of a single FEM-3 module to 40 and more grams of oxidants per hour. However, specific salt consumption remains the same – about 1.7 g/g in all regimes. Another way of increasing chlorine dioxide and ozone content is alkalization of initial saline solution up to ðÍ = 9.5-10.5. Three-year experience of AQUACHLOR devices operation in various conditions (climatic, technical, technological) in Russia and abroad demonstrated their high efficiency, cost-effectiveness, and practically complete absence of chlorination by-products even during treatment with oxidant solution of wastewaters with high organic compound content. A method of producing disinfectant solution and a device to implement it.RF Patent # 2208589. Filed 03.08.2001, published 20.07.2003. Bakhir V.M., Zadorozhny Yu.G., Panicheva S.A. When FEM-3 modules in an RPE reactor are hydraulically connected in parallel, the reactor’s specific parameters and operational characteristics generally precisely correspond to the parameters and characteristics of a single FEM-3 module. This makes it possible to competently develop engineering electrochemical systems with RPE reactors of required capacity on the basis of similar parameters for a single FEM-3 module working in the corresponding regime. Based on well-known facts that mass m of substances engaged in electrochemical reactions is determined by consumed electricity amount Qe: m = q ´ Qe, where Qe = I ´ t ; q = M/nF, and that given the same electricity amount power Wm consumed during the process is determined only by voltage value U: Wm = I ´ U ´ t , where U = Udecomp. + Upol + I ´ R, investigations were conducted using various electrochemical systems of the relationship between the degree of deviation of physico-chemical parameters of activated solution from equilibrium state (degree of solution meta-stability), intensity and depth of electrochemical impact, as well as initial solution mineralization. The investigations demonstrated that meta-stable (relaxing in time) properties and physical-chemical parameters of anolyte and catholyte produced in conditions of equal specific electricity consumption depended on the degree of electrochemical exposure nonequilibrium, and not on electrolysis laws. Most essentially, meta-stability degree of diluted sodium chloride aqueous solution is affected by the mechanism of charge transfer through the diaphragm of a flow-through electrochemical reactor, depending on the ratio of specific electricity amount and initial water mineralization. At I/Q < F´ cNaCl, hydroxyl (OH- ) and hydroxonium (H+ ) ions practically do not participate in charge transfer through the diaphragm due to their low concentration in comparison with that of chlorine anions and sodium cations. At I/Q @ F´ cNaCl all ions present in the initial solution take part in charge transfer. At I/Q > F´ cNaCl charge transfer is performed only by hydroxyl (OH- ) and hydroxonium (H+ ) ions. Investigations of single FEM-3 modules showed that in the process of ANK anolyte production according to a flow-sheet envisaging direct-flow movement of solutions in electrode chambers, anolyte oxidant concentration is on the average 15% lower than under counterflow of solutions in electrode chambers. Besides, it was found that regulation of ANK anolyte ðÍ by discharging part of catholyte was more efficient with solutions’ moving in counterflow, since in that case the required volume of discharged catholyte decreased on the average by 20% as compared to a flow-sheet with direct flow (that is, in one direction) of solutions in the electrode chambers of FEM-3 module. Based on the analysis of experimental research, the flow sheet of ANK anolyte production engaging two hydraulically and consecutively connected FEM-3 modules in a counterflow regime described in the patent was developed. It was found that such FEM modules’ connection makes it possible to develop an efficient reactor for ANK anolyte production from initial sodium chloride solution of less than 2.5 g/l concentration and 500-600 mg/l oxidants’ content. Bearing in mind that the general mineralization/oxidant concentration ratio of ANK anolyte produced by STEL-10Í-120-01 and STEL-60-03-ÀÍÊ devices lies within the limits of 10-15, and the corresponding parameter for ECA-30-type devices by far surpasses those figures, the general mineralization/oxidant concentration ratio of ANK anolyte produced by reactor with two consecutively connected FEM-3 modules varies between 5 and 7, which is an important factor of decreasing anolyte corrosive ability. ANK anolyte with the latter-indicated values of the general mineralization (which generally corresponds to sodium chloride concentration in the initial solution) / oxidant concentration ratio is called ANK anolyte with mean specific oxidant content, as distinct from ANK anolyte with the above parameters’ ratio of 10 and higher, which is designated ÀNÊ anolyte with low specific oxidant content. A disinfectant agent.RF Patent # 2249466.Filed 26.05.2003, published 10.04.2005. Panicheva S.A., Bakhir V.M., Zadorozhny Yu.G., Leonov B.I. The disinfectant agent is produced by adding a small amount (from 0.1 to 5.0 volume percent) of ethyl alcohol into low-mineralized ANK anolyte with high specific oxidant content. This results in 1,000 to 10,000-fold increase of antimicrobial anolyte activity as compared to similar ANK anolyte with no ethyl alcohol added. Anolyte with added alcohol is very efficient in conditions of high protein loading and can be used to decontaminate even porous rubber and plastic surfaces covered with dried up protein film. A device for disinfecting swimming pool water.RF Patent # 38336 for a useful model. Filed 24.02.2004, published 10.06.2004. Barabash T.B., Bakhir V.M., Vtorenko V.I., Zadorozhny Yu.G., Tranov V.N. Trade name of the given device is ALLIGATOR device. The device is meant for decontaminating water in 30-150 cu. m. swimming pools. The principle of ALLIGATOR device operation is that antimicrobial substances are generated from swimming pool water proper thanks to treating its small amount in the electrochemical reactor of the device. Water saturated with bactericidal substances formed in the device is mixed with the main bulk of water and ensures its decontamination. Characteristic features of ALLIGATOR device operation are no chlorine odor over the water surface, complete exclusion of skin and eyes irritation, ideal water clarity and its favorable effect on the human body thanks to ozone and oxygen present in the water. ALLIGATOR device guarantees non-chemical saturation of swimming pool water with ecologically safe disinfectants: ozone, hydrogen peroxide, atomic oxygen, hypochlorous acid and some others generated in the device reactor, through which a small amount of water flows pumped over by a circulation pump. The owner of the swimming pool where the pilot ALLIGATOR model was tested, prior to ALLIGATOR use, every month spent about USD 100 to purchase hypochlorite made by Contec, and permanently used a 2 kW ultrasonic device and 3 kW UV water irradiation device. However, swimming pool walls still grew moldy (at the corners), and water had a disagreeable chlorine odor. After he began to use ALLIGATOR device, the owner switched off the ultrasonic and UV devices and stopped purchasing hypochlorite. On the second day, mold in the swimming pool disappeared, water is always ideally clear and pure, smells fresh, is nice to be in, and according to the owner’s wife it has become “velvety”. |
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